CN114807989A - Synthesis method of 9-bromo-10- (2-naphthyl) anthracene - Google Patents
Synthesis method of 9-bromo-10- (2-naphthyl) anthracene Download PDFInfo
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- CN114807989A CN114807989A CN202210410984.5A CN202210410984A CN114807989A CN 114807989 A CN114807989 A CN 114807989A CN 202210410984 A CN202210410984 A CN 202210410984A CN 114807989 A CN114807989 A CN 114807989A
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- anthracene
- bromide
- bromination
- bromo
- naphthyl
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- FKIFDWYMWOJKTQ-UHFFFAOYSA-N 9-bromo-10-naphthalen-2-ylanthracene Chemical compound C12=CC=CC=C2C(Br)=C(C=CC=C2)C2=C1C1=CC=C(C=CC=C2)C2=C1 FKIFDWYMWOJKTQ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000001308 synthesis method Methods 0.000 title claims description 10
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 bromine free radical Chemical class 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 14
- 238000005899 aromatization reaction Methods 0.000 claims abstract description 13
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 7
- 239000000376 reactant Substances 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 10
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 claims description 9
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 5
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical group CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001622 calcium bromide Inorganic materials 0.000 claims description 2
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 claims description 2
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 claims description 2
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 claims description 2
- OLSRDHGDHZNHLZ-UHFFFAOYSA-M dodecane-1-sulfonate tetrabutylazanium Chemical compound C(CCC)[N+](CCCC)(CCCC)CCCC.C(CCCCCCCCCCC)S(=O)(=O)[O-] OLSRDHGDHZNHLZ-UHFFFAOYSA-M 0.000 claims description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N methyl monoether Natural products COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052794 bromium Inorganic materials 0.000 abstract description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 7
- 230000031709 bromination Effects 0.000 abstract description 6
- 238000005893 bromination reaction Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract description 2
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 2
- 230000000977 initiatory effect Effects 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 150000003254 radicals Chemical class 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 230000000911 decarboxylating effect Effects 0.000 abstract 1
- 238000004809 thin layer chromatography Methods 0.000 description 12
- 239000012043 crude product Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 150000001454 anthracenes Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- BRUOAURMAFDGLP-UHFFFAOYSA-N 9,10-dibromoanthracene Chemical compound C1=CC=C2C(Br)=C(C=CC=C3)C3=C(Br)C2=C1 BRUOAURMAFDGLP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LXTKCTMGEWVPTB-UHFFFAOYSA-N butylazanium;acetate Chemical group CC(O)=O.CCCCN LXTKCTMGEWVPTB-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/11—Halogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/03—Acyclic or carbocyclic hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/27—Halogenation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/29—Coupling reactions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing 9-bromo-10- (2-naphthyl) anthracene, which comprises the following steps: anthracene and beta-naphthoic acid are used as initial reactants, bromide, a solvent and an electrolyte are added, and the 9-bromo-10- (2-naphthyl) anthracene is obtained through arylation-bromination-aromatization under an electrocatalysis system. The method does not need to carry out pre-modification bromination on a substrate, does not have classical Suzuki coupling operation, avoids metal residues, adopts commercially available anthracene and beta-naphthoic acid as reaction raw materials, adopts a green and oxidant-free electrocatalysis system, realizes the arylation-bromination-aromatization process under the initiation of free radicals by a one-pot method, and has good selectivity; the method comprises the steps of utilizing electrocatalysis to realize a single electron transfer process to obtain a bromine free radical, then generating an HAT process, decarboxylating to obtain a beta-naphthalene free radical, then performing interconversion with anthracene, oxidizing to obtain benzyl positive ions, then capturing bromine, and finally performing dehydrogenation to realize an aromatization process.
Description
Technical Field
The invention belongs to the technical field of anthracene blue light materials, and particularly relates to a synthesis method of 9-bromo-10- (2-naphthyl) anthracene.
Background
Organic Light Emitting Diodes (OLEDs) are known as the star flat panel displays in the 21 st century and are also known as the ultimate displays in the future due to their advantages of large viewing angle, low voltage, low power consumption, and being foldable. Among the numerous luminescent materials, blue materials have affected the development of the entire panel due to their lifetime and efficiency issues, and anthracene-based compounds are desirable synthetic segments for blue materials.
The prior-art classic anthracene material also has a plurality of problems: for example, highly symmetric anthracene derivatives are easy to crystallize and unstable in film morphology, and thus how to realize asymmetric synthesis of anthracene derivatives is a hot point of research in OLEDs. The synthesis of the asymmetric anthracene brominated compound at the present stage is mainly through selective coupling, wherein,
the first method is selective single naphthalene cyclization modification of 9, 10-dibromoanthracene (see the following reaction formula), and the construction of a C-C bond is realized by adopting a classical Suzuki coupling mode, but for a dibromo compound, the selective bromine retention difficulty is large, and the subsequent purification difficulty and yield are also aggravated.
In the method II, the 9-bromo-10- (2-naphthyl) anthracene is synthesized by bromination after the anthracene precursor containing the naphthalene ring is synthesized in advance, namely, the target product can be synthesized by utilizing the bromination process (see the following reaction formula). However, the synthesis process of the precursor still depends on a coupling mode, the whole reaction path is further increased, in addition, the cost of raw materials is higher than that of the method I, and in addition, NBS (N-bromosuccinimide) is generally used as a bromine source or other oxidation systems in the bromination at the present stage, so the reaction cost is further increased.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
The invention aims to provide a synthesis method of 9-bromo-10- (2-naphthyl) anthracene, which solves the problems of high selective bromine retention difficulty, high purification difficulty and low yield, and solves the problems that a bromine source or an oxidation system is required to be used in a bromination stage and the reaction cost is high in the prior art.
In order to achieve the above object, the present invention provides a method for synthesizing 9-bromo-10- (2-naphthyl) anthracene, comprising the steps of: anthracene and beta-naphthoic acid are taken as initial reactants, then bromide, solvent and electrolyte are added, and the 9-bromo-10- (2-naphthyl) anthracene is obtained through arylation-bromination-aromatization under an electrocatalysis system; the reaction formula is as follows:
the method takes commercially available anthracene and beta-naphthoic acid as basic reaction raw materials, adopts a green and oxidant-free electrocatalysis system, and utilizes electrocatalysis to realize a single electron transfer process to complete chemical bond construction.
In an embodiment of the present invention, the bromide is selected from any one or more of potassium bromide, hydrobromic acid, sodium bromide, ammonium bromide, magnesium bromide, calcium bromide, cobalt bromide and manganese bromide. Preferably, the bromide is selected from any one of potassium bromide, hydrobromic acid and sodium bromide.
In one embodiment of the present invention, the solvent is selected from any one of dichloromethane, dichloroethane, chloroform, chlorobenzene, tetrahydrofuran, toluene, xylene, methanol, hexafluoroisopropanol, N-Dimethylformamide (DMF), N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, tert-butyl dimethyl ether, 1, 4-dioxane, acetone, acetonitrile, and ethyl acetate; preferably, the solvent is selected from any one of hexafluoroisopropanol, N-Dimethylformamide (DMF), and acetonitrile.
In one embodiment of the present invention, the electrolyte is butyl ammonium acetate, ammonium tetra-tert-butyl dodecyl sulfonate, p-toluenesulfonic acid monohydrate, tetrabutyl ammonium tetrafluoroborate, tetrabutyl ammonium hexafluorophosphate, tetrabutyl amine hydroxide, tetra-tert-butyl ammonium acetate; preferably, the electrolyte is selected from one or more of tetrabutylammonium acetate, tetrabutylammonium dodecylsulfonate, p-toluenesulfonic acid monohydrate and tetrabutylammonium tetrafluoroborate.
In one embodiment of the present invention, the molar ratio of anthracene to β -naphthoic acid is 1 (0.5 to 3); preferably, the molar ratio of anthracene to beta-naphthoic acid is 1 (1-1.2).
In one embodiment of the present invention, the specific steps of arylation-bromination-aromatization under an electrocatalytic system are as follows: adding anthracene, beta-naphthoic acid, bromide, electrolyte and solvent into a reaction bottle; then two electrodes are inserted, and the power is supplied, the current is adjusted, and the arylation-bromination-aromatization reaction is carried out.
In one embodiment of the present invention, the reaction time of the arylation-bromination-aromatization is 4 to 10 hours.
In an embodiment of the present invention, the electrode is any one of a platinum negative electrode + carbon positive electrode, a lead negative electrode + platinum positive electrode, and a carbon negative electrode + carbon positive electrode.
In one embodiment of the present invention, the obtained 9-bromo-10- (2-naphthyl) anthracene is further subjected to extraction and recrystallization.
In one embodiment of the invention, extraction is carried out with water and ethyl acetate.
Compared with the prior art, the invention has the following beneficial effects:
the synthesis method of 9-bromo-10- (2-naphthyl) anthracene adopts commercially available and cheap anthracene and beta-naphthoic acid as basic reaction raw materials, adopts a green and oxidant-free electrocatalysis system, realizes an arylation-bromination-aromatization process under the initiation of free radicals by a one-pot method, and has good selectivity; the method comprises the steps of utilizing electrocatalysis to realize a single electron transfer process to obtain a bromine free radical, then generating an HAT (hydrogen atom transfer mechanism) process, obtaining a beta-naphthalene free radical in a decarboxylation process, then performing interconversion with anthracene, oxidizing to obtain benzyl positive ions, then capturing bromine, and finally performing dehydrogenation to realize an aromatization process.
Compared with the prior art, the method has the advantages that pre-modification bromination is not required to be carried out on the substrate, and classical Suzuki coupling operation is not required, so that metal residue is avoided; the method has the advantages of mild reaction conditions, simple and easily-obtained raw materials, simple operation, no need of adding a bromine source, an oxidant and a metal reagent into the system, and cleaner, greener and more efficient system.
Detailed Description
The following detailed description of specific embodiments of the invention is provided, but it should be understood that the scope of the invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
Example 1
A method for synthesizing 9-bromo-10- (2-naphthyl) anthracene comprises the following specific steps:
8.91g of refined anthracene (Mr. 178.23, 99%, 0.05mol), 8.61g of 2-naphthoic acid (Mr. 172.18, 99%, 0.05mol), 11.12g of hydrobromic acid (Mr. 80.91, 40%, 0.055mol), 15.08g of tetrabutylammonium acetate (Mr. 301.51, 99%, 0.05mol) were placed in a 100mL four-necked flask at room temperature, and 40mL of DMF was added; then, inserting a platinum electrode and a carbon electrode below the liquid level to serve as a cathode and an anode, adjusting the current to 15mA, reacting for 4 hours, and monitoring by Thin Layer Chromatography (TLC); after the reaction was completed, water (100 mL) and ethyl acetate (200 mL) were added for extraction, and the organic layer was desolventized to obtain a crude product, which was recrystallized from dichloroethane to obtain 7.22g of 9-bromo-10- (2-naphthyl) anthracene with a yield of 37.8%.
Example 2
A method for synthesizing 9-bromo-10- (2-naphthyl) anthracene comprises the following specific steps:
8.91g of refined anthracene (Mr. 178.23, 99%, 0.05mol), 8.61g of 2-naphthoic acid (Mr. 172.18, 99%, 0.05mol), 7.14g of potassium bromide (Mr. 119, 99%, 0.06mol), 16.46g of tetrabutylammonium tetrafluoroborate (Mr. 329.27, 99%, 0.05mol) and 40mL of acetonitrile were charged into a 100mL four-neck flask at room temperature; then, inserting a lead electrode and a platinum electrode below the liquid level to serve as a cathode and an anode, adjusting the current to 15mA, reacting for 6h, and monitoring by Thin Layer Chromatography (TLC); after the reaction was completed, water (100 mL) and ethyl acetate (200 mL) were added for extraction, and the organic layer was desolventized to obtain a crude product, which was recrystallized from dichloroethane to obtain 8.35g of 9-bromo-10- (2-naphthyl) anthracene with a yield of 43.7%.
Example 3
A method for synthesizing 9-bromo-10- (2-naphthyl) anthracene comprises the following specific steps:
8.91g of refined anthracene (Mr. RTM. 178.23, 99%, 0.05mol), 8.61g of 2-naphthoic acid (Mr. RTM. 172.18, 99%, 0.05mol), 7.14g of potassium bromide (Mr. RTM. 119, 99%, 0.06mol), 9.51g of p-toluenesulfonic acid monohydrate (Mr. RTM. 190.2, 99%, 0.05mol) were placed in a 100mL four-necked flask at room temperature, and 40mL of acetonitrile was added; then, inserting a lead electrode and a platinum electrode below the liquid level to serve as a cathode and an anode, adjusting the current to 15mA, reacting for 8 hours, and monitoring by Thin Layer Chromatography (TLC); after the reaction was completed, water (100 mL) and ethyl acetate (200 mL) were added for extraction, and the organic layer was desolventized to obtain a crude product, which was recrystallized from dichloroethane to obtain 8.35g of 9-bromo-10- (2-naphthyl) anthracene with a yield of 45.7%.
Example 4
A method for synthesizing 9-bromo-10- (2-naphthyl) anthracene comprises the following specific steps:
8.91g of refined anthracene (Mr. RTM. 178.23, 99%, 0.05mol), 10.33g of 2-naphthoic acid (Mr. RTM. 172.18, 99%, 0.06mol), 6.17g of sodium bromide (Mr. RTM. 102.89, 99%, 0.06mol), 16.11g of ammonium tetra-tert-butyldodecylsulfonate (Mr. RTM. 322.37, 99%, 0.05mol) were placed in a 100mL four-necked flask at room temperature, and 40mL of hexafluoroisopropanol was added; then, inserting a platinum electrode and a graphite electrode below the liquid level to serve as a cathode and an anode, adjusting the current to 15mA, reacting for 10 hours, and monitoring by Thin Layer Chromatography (TLC); after the reaction was completed, water (100 mL) and ethyl acetate (200 mL) were added for extraction, and the organic layer was desolventized to obtain a crude product, which was recrystallized from dichloroethane to obtain 18.18g of 9-bromo-10- (2-naphthyl) anthracene with a yield of 95.2%.
Example 5
8.91g of refined anthracene (Mr. 178.23, 99%, 0.05mol), 9.47g of 2-naphthoic acid (Mr. 172.18, 99%, 0.055mol), 7.14g of potassium bromide (Mr. 119, 99%, 0.06mol), 16.11g of ammonium tetra-tert-butyldodecylsulfonate (Mr. 322.37, 99%, 0.05mol) were placed in a 100mL four-necked flask at room temperature, and 40mL of DMF was added; then, inserting a lead electrode and a platinum electrode below the liquid level to serve as a cathode and an anode, adjusting the current to 15mA, reacting for 8 hours, and monitoring by Thin Layer Chromatography (TLC); after the reaction was completed, water (100 mL) and ethyl acetate (200 mL) were added for extraction, and the organic layer was desolventized to obtain a crude product, which was recrystallized from dichloroethane to obtain 12.55g of 9-bromo-10- (2-naphthyl) anthracene with a yield of 65.7%.
Example 6
8.91g of refined anthracene (Mr. RTM. 178.23, 99%, 0.05mol), 10.33g of 2-naphthoic acid (Mr. RTM. 172.18, 99%, 0.06mol), 7.14g of potassium bromide (Mr. RTM. 119, 99%, 0.06mol), 16.11g of ammonium tetra-tert-butyldodecylsulfonate (Mr. RTM. 322.37, 99%, 0.05mol) were placed in a 100mL four-necked flask at room temperature, and 40mL of acetonitrile was added; then, inserting a lead electrode and a platinum electrode below the liquid level to serve as a cathode and an anode, adjusting the current to 15mA, reacting for 8 hours, and monitoring by Thin Layer Chromatography (TLC); after the reaction was completed, water (100 mL) and ethyl acetate (200 mL) were added for extraction, and the organic layer was desolventized to obtain a crude product, which was recrystallized from dichloroethane to obtain 15.05g of 9-bromo-10- (2-naphthyl) anthracene in 78.8% yield.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. A method for synthesizing 9-bromo-10- (2-naphthyl) anthracene, which is characterized by comprising the following steps: anthracene and beta-naphthoic acid are taken as initial reactants, then bromide, solvent and electrolyte are added, and the 9-bromo-10- (2-naphthyl) anthracene is obtained through arylation-bromination-aromatization under an electrocatalysis system; the reaction formula is as follows:
2. the synthesis method according to claim 1, wherein the bromide is selected from any one or more of potassium bromide, hydrobromic acid, sodium bromide, ammonium bromide, magnesium bromide, calcium bromide, cobalt bromide and manganese bromide; preferably, the bromide is selected from any one of potassium bromide, hydrobromic acid and sodium bromide.
3. The synthesis method according to claim 1, wherein the solvent is selected from any one of dichloromethane, dichloroethane, chloroform, chlorobenzene, tetrahydrofuran, toluene, xylene, methanol, hexafluoroisopropanol, N-Dimethylformamide (DMF), N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, tert-butyl dimethyl ether, 1, 4-dioxane, acetone, acetonitrile and ethyl acetate; preferably, the solvent is selected from any one of hexafluoroisopropanol, N-Dimethylformamide (DMF), and acetonitrile.
4. The method of synthesis according to claim 1, wherein the electrolyte is tetrabutylammonium acetate, tetrabutylammonium dodecylsulfonate, p-toluenesulfonic acid monohydrate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium acetate, tetrabutylammonium hydroxide; preferably, the electrolyte is selected from any one or more of tetrabutylammonium acetate, ammonium tetra-tert-butyldodecylsulfonate, p-methylbenzenesulfonic acid monohydrate, and tetrabutylammonium tetrafluoroborate.
5. The synthesis method of claim 1, wherein the molar ratio of anthracene to beta-naphthoic acid is 1 (0.5-3); preferably, the molar ratio of the anthracene to the beta-naphthoic acid is 1 (1-1.2).
6. The synthesis process according to claim 1, characterized in that the specific steps of arylation-bromination-aromatization under electrocatalytic system are: adding anthracene, beta-naphthoic acid, bromide, electrolyte and solvent into a reaction bottle; then two electrodes are inserted, and the power is supplied, the current is adjusted, and the arylation-bromination-aromatization reaction is carried out.
7. The synthesis process according to claim 1 or 6, characterized in that the reaction time of arylation-bromination-aromatization is 4-10 h.
8. The synthesis method according to claim 6, wherein the electrode is any one of a platinum negative electrode + carbon positive electrode, a lead negative electrode + platinum positive electrode, and a carbon negative electrode + carbon positive electrode.
9. The synthesis method according to claim 1, wherein the obtained 9-bromo-10- (2-naphthyl) anthracene is further subjected to extraction and recrystallization.
10. The method of claim 9, wherein the extraction is performed with water and ethyl acetate.
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| US20150053946A1 (en) * | 2013-08-22 | 2015-02-26 | Samsung Display Co., Ltd. | Anthracene-based compounds and organic light-emitting device including the same |
| WO2020111733A1 (en) * | 2018-11-30 | 2020-06-04 | 주식회사 엘지화학 | Organic light emitting device |
| CN112142674A (en) * | 2020-09-27 | 2020-12-29 | 陕西莱特迈思光电材料有限公司 | Organic compound, and electronic element and electronic device using same |
| CN113264911A (en) * | 2021-04-30 | 2021-08-17 | 烟台显华化工科技有限公司 | Compound, organic light-emitting material and organic electroluminescent device |
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| US20150053946A1 (en) * | 2013-08-22 | 2015-02-26 | Samsung Display Co., Ltd. | Anthracene-based compounds and organic light-emitting device including the same |
| WO2020111733A1 (en) * | 2018-11-30 | 2020-06-04 | 주식회사 엘지화학 | Organic light emitting device |
| CN112142674A (en) * | 2020-09-27 | 2020-12-29 | 陕西莱特迈思光电材料有限公司 | Organic compound, and electronic element and electronic device using same |
| CN113264911A (en) * | 2021-04-30 | 2021-08-17 | 烟台显华化工科技有限公司 | Compound, organic light-emitting material and organic electroluminescent device |
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